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electrothermomechanical actuators
Il’Ya A. Gural’Skiy, Carlos Mario Quintero, José Sánchez Costa, Philippe
Demont, Gabor Molnar, Lionel Salmon, Helena J. Shepherd, Azzedine
Bousseksou
Composites of the spin crossover complex [Fe(trz)(H-trz)2](BF4) (H-trz ¼ 1,2,4-4H-triazole and trz ¼ 1,2,4-
triazolato) dispersed in a poly(methylmethacrylate) (PMMA) matrix were synthesized and investigated for
their spin crossover properties by optical reflectivity, Raman spectroscopy and calorimetry. These
composite films were used to fabricate bilayer cantilevers that can perform efficient and tuneable
mechanical actuation based on the spin transition. A prototype device that uses the spin transition
phenomenon to convert electrical energy into mechanical motion through Joule heating is described.
This device is used to perform oscillatory actuation driven by a modulated current. The ability to tune the
performance of this electromechanical system is demonstrated by varying the working temperature, the
applied ac current and its frequency.
during the transition between their high spin (HS) and low spin
Introduction (LS) electronic congurations.7,8 Despite copious investigations
The transformation of electrical energy into motion is one of the into their magnetic and optical properties, the spontaneous
main demands from micro- and nanoelectromechanical linear strain (3) that can reach 8% (ref. 9 and 10) in these
systems (MEMS and NEMS).1 This conversion could be achieved materials seems to be one of the most fascinating assets for
via electrostatic2 or piezoelectric effects,3 Joule heating,4 etc. practical applications.11 The 3 values in SCO complexes are high
Among these methods electrothermal actuation is a widely used when compared to analogous phase transition materials. For
approach due to its simplicity both for the fabrication process example, in the very promising VO2 known for the reversible
and the actuation mechanism.5 The choice of the actuating metal–insulator phase change, a linear strain up to 2% can be
material is a crucial step in the construction of a new electro- reached.12–16 Another important asset is that SCO can be
mechanical system and the numerous specic requirements provoked by different external stimuli such as temperature,
make the development of novel actuating materials necessary.6 pressure, magnetic eld, excitation with light or adsorption of
For instance, the energy density of a mechanical actuator is chemical species. The interest is additionally supported by the
basically dependent on the strain that can be generated in its existence of hundreds of SCO complexes reported to date with
active materials. However, many other important performance different transition temperatures, hysteresis and abruptness of
indicators, such as the displacement, the force, actuation speed the spin transition.7 This versatility can be further extended by
(or frequency) and energy efficiency will also depend on the the elaboration of composite materials. For example, SCO
material selection. compounds have been imbedded in silica17–19 and various
Spin crossover (SCO) complexes of 3d4–3d7 transition metal polymer20–25 matrices providing nanoscale connement and/or
ions are well known for changing a variety of physical properties better processability.
Recently we reported on the application of spin crossover
a
LCC, CNRS & University of Toulouse (UPS, INPT), 205 route de Narbonne, 31077 materials for the elaboration of bimorph cantilevers, which
Toulouse, France. E-mail: azzedine.bousseksou@lcc-toulouse.fr were actuated both thermally and by light irradiation.11 As a
b
Department of Chemistry, Taras Shevchenko National University of Kyiv, 64 proof of concept, a single crystal of the SCO complex
Volodymyrska Street, 01601 Kyiv, Ukraine {Fe(3-CNpy)[Au(CN)2]2}$2/3H2O (py ¼ pyridine) was covered
c
LAAS, CNRS & Université de Toulouse (UPS, INSA, IAES), 7 avenue du colonel Roche, with a layer of Al and used as a cantilever actuator. A reversible
31077 Toulouse, France
d
movement of this bimorph was reached as a result of thermally
Institut Carnot CIRIMAT, CNRS & Université de Toulouse III, 118 Route de Narbonne,
31062 Toulouse, France
and photo-induced spin transitions, thus revealing a novel
e
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK. E-mail: h.j. mechanism of actuation that opens up perspectives for the
shepherd@bath.ac.uk development of MEMS, articial muscles and other applica-
† Electronic supplementary information (ESI) available: Actuation of a cantilever tions for the harvesting and transformation of energy (thermal,
with a different geometry, detailed theoretical calculations, movie of the cantilever electric, photonic, .). Additionally, three bilayer polymer/SCO
oscillation. See DOI: 10.1039/c4tc00267a
composite devices, each with different SCO compounds, were and cannot be removed from the substrate or further processed.
developed to demonstrate the versatility of SCO materials for The spin transition properties of these composites were
actuating tasks. In this paper we go further by describing a observed and analyzed by optical microscopy since the SCO is
prototype device that can exploit the spin transition phenom- accompanied by a drastic change of color in the active complex
enon to convert electrical energy into motion via Joule heating from pink in the LS state to colorless in the HS state. This effect
in a composite bilayer actuator. is associated with the reversible bleaching of the characteristic
1
A1 / 1T1 absorption band centered around l ¼ 550 nm. Fig. 1
Results and discussion reveals a strong thermal dependence of the composite color that
is clearly associated with the HS 4 LS spin transition. The SCO
SCO/polymer composites in the composites takes place within the same region of
Even though the application of a single crystal SCO material for temperature as for the pure complex. The transition curves of
the construction of bimorph cantilevers was found efficient and the composites were found to be relatively independent of the
the behavior of these actuators is easy to rationalize from a polymer/complex ratio; the most signicant differences being a
theoretical point of view, the practical use of such systems has slight loss of abruptness of the spin transition for composites
certain limitations. This is mostly related to the serendipity of with lower loadings of the active material. This observation may
the crystal growth. In contrast, techniques for employing poly- simply be related to the lower thermal conductivity of the
mers and polymer composites in MEMS design are well devel- polymer component compared to the coordination compound.
oped.26 Hence, we synthesized a polymer composite material, While the SCO behaviour of composite materials is in general
consisting of the spin crossover complex [Fe(trz)(H-trz)2](BF4) not easy to predict, the negligible inuence of a polymer matrix
(form 1b, one of the two forms described by Kröber et al.27) and on those properties, as shown here, is certainly not
the organic polymer PMMA, which can produce continuous unprecedented.20–23
lms of several microns in thickness over a large area. This Selected Raman spectra of [Fe(trz)(H-trz)2](BF4) and the
iron(II) compound is known for its abrupt and robust spin PMMA/[Fe(trz)(H-trz)2](BF4) composite (50% loading) recorded
transition that takes place with a large thermal hysteresis at 20 C and 110 C are shown in Fig. 2. In the low frequency
around 85 C on heating and 60 C on cooling. It is important to region (100–300 cm1), very signicant changes are observed
note also that in this particular SCO complex the transition is upon the SCO. As discussed in ref. 29, the modes at 300, 288,
accompanied by a volume change of 11%.28 211, 202 cm1 are attributed to the LS state of the complex,
A series of PMMA/1b composites with different relative whereas those at 186 and 109 cm1 are associated with the HS
proportions of the active complex were fabricated by mechan- state. These changes of the vibrational frequencies accompa-
ical dispersion of the powder of 1b in a PMMA solution with nying the spin transition are a general trend and originate from
subsequent evaporation of the chloroform solvent. A drop- the strong electron–lattice coupling in these systems.7 The
casting procedure allows the deposition of the composite lms disappearance of the characteristic LS/HS modes at high/low
over different surfaces. Films with different proportions (10– temperatures allows us to conclude that the spin transition is
50%) of the active complex were produced (Fig. 1). Loading in virtually complete in both directions for the isolated complex as
excess of 50% of the SCO complex results in lms that are brittle well as for the composite material.
Fig. 8 Amplitude of the bilayer cantilever oscillation at different maximum value) at fcut off z 0.5 Hz (Fig. 9). In this case the
temperatures. The ac current and frequency were fixed (Imax ¼ 300 completeness of the transition in both directions (LS to HS and
mA, f ¼ 0.1 Hz). Insets: tip position of the cantilever as a function of HS to LS) is limited by the rate of heat diffusion; there is
time at selected temperatures.
insufficient time for the device to reach the required tempera-
ture to switch all active centers. For this actuator there is no
frequency limitation up to f ¼ 0.1 Hz; however, no movement is
not result in any signicant actuation of the cantilever. This observed for f > 1 Hz. This limitation is clearly related to the heat
threshold effect is likely to be the result of insufficient heating, transfer processes and not to the spin conversion process that
i.e. below a certain temperature the nucleation of the HS phase has much faster dynamics.7,8
cannot take place. The low amplitude oscillation observed for The observed cut-off frequency is not a fundamental limit, but
currents below this value should be considered chiey as a rather denotes that (if necessary) the device must be operated at a
thermal expansion effect without SCO. By contrast, a current over different temperature and/or a different current should be
200 mA generates enough heat to induce the thermal SCO, applied. Even more importantly, the cantilever geometry and the
reaching a maximum amplitude of actuation at Imax z 300 mA. thermalisation conditions can also drastically change the
The deection at currents between 200 and 300 mA corresponds performance of these actuators in terms of actuating speed. One
to a partial spin transition of the Fe(II) complex in the composite. example describing the effect of a different geometry is shown in
This threshold current value can be tuned via several different the ESI (Fig. S1–S3†). A cantilever of a smaller size was fabricated
approaches, including the change of SCO active complex. Indeed, and studied in a similar manner. A direct consequence of the size
the use of any SCO compound with higher/lower temperature of reduction is the faster heat exchange between the cantilever and
transition should increase/decrease the critical value of current its surroundings. Thus, a lower cut-off temperature and current,
necessary to drive the cantilever oscillation. as well as a higher cut-off frequency were observed.
Measurements at constant f and Imax reveal a clear dependence
of the actuation amplitude on the surrounding temperature as
shown in Fig. 8. Up to 50 C a slight and almost linear diminution Experimental information
of the actuating amplitude is observed and can be explained by an
incomplete HS to LS transition when the current is switched off. PMMA (Mw ¼ 550 000), iron(II) tetrauoroborate hexahydrate,
Above 50 C an abrupt drop off in amplitude is observed, due to 1-H-1,2,4-triazole and chloroform were purchased from Sigma
the thermal SCO occurring above this point. Thus, even when Aldrich and used without any further purication. Conductive
there is no current applied to the cantilever, a signicant fraction silver paint RS 186-3593 was purchased from RS Components.
of the active SCO complex remains in the HS state. This paint contains a polymeric basis lled with silver micro-
Again, this characteristic cut-off temperature can be tuned by spheres (<18 mm, 56%) and dissolved in an n-butyl acetate/
substituting the active complex for another SCO material. The 2-methoxy-1-methylethyl acetate mixture.
abrupt on/off switch of the actuation with temperature can be [Fe(trz)(H-trz)2](BF4) (form 1b) was prepared from
achieved by using highly cooperative spin crossover systems Fe(BF4)2$6H2O and 1-H-1,2,4-triazole according to the procedure
where the spin state change occurs sharply within < 1 K. (N.B. To described by Kröber et al.27 The active composite material was
observe an abrupt cut-off as a function of temperature efficient elaborated by mechanical dispersion of the [Fe(trz)(H-trz)2](BF4)
thermalization is also necessary.) On the other hand, the use of powder (5 mg) in a solution of PMMA (5 mg) in CHCl3 (200 ml).
compounds with a gradual SCO – taking place within hundreds This suspension was drop-casted onto a silicon substrate (1 1
degrees – can allow ne control over the actuation amplitude by cm2) and allowed to dry. 150 ml of the conductive paint was
changing the environmental temperature. subsequently spin coated (2000 rpm, 3000 rpss, 30 s) onto the
Varying the frequency at constant Imax and T reveals a cut-off upper surface. The resulting bilayer lm was removed from the
of the actuation (dened as a decay in amplitude of 0.707 of the substrate and cut into cantilevers. The cantilever used was 6.7
mm in length and 1 mm in width. The thicknesses of the SCO Notes and references
and conductive layers were ca. 100 and 50 mm, respectively.
Variable temperature Raman spectra of the samples were 1 M. Bao, in Analysis and Design Principles of MEMS Devices,
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Acknowledgements 24 J. Larionova, L. Salmon, Y. Guari, A. Tokarev, K. Molvinger,
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Financial support from the project Switchelec (ANR-12-IS07- 47, 8236–8240.
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